EP3768743B1 - Etheraminmischung bestehend aus polyetherdiaminen und verfahren zu ihrer herstellung und verwendung - Google Patents

Etheraminmischung bestehend aus polyetherdiaminen und verfahren zu ihrer herstellung und verwendung

Info

Publication number
EP3768743B1
EP3768743B1 EP19772328.1A EP19772328A EP3768743B1 EP 3768743 B1 EP3768743 B1 EP 3768743B1 EP 19772328 A EP19772328 A EP 19772328A EP 3768743 B1 EP3768743 B1 EP 3768743B1
Authority
EP
European Patent Office
Prior art keywords
diol
epoxy resin
etheramine mixture
resin system
hydrophobic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP19772328.1A
Other languages
English (en)
French (fr)
Other versions
EP3768743A1 (de
EP3768743A4 (de
Inventor
Howard P. Klein
Terry L. Renken
Cheng-Kuang Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Petrochemical LLC
Original Assignee
Huntsman Petrochemical LLC
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Publication date
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Publication of EP3768743A1 publication Critical patent/EP3768743A1/de
Publication of EP3768743A4 publication Critical patent/EP3768743A4/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • C08G65/3255—Ammonia
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02—Polyureas

Definitions

  • the present disclosure generally relates to an etheramine mixture consisting of one or more polyether diamines, methods for its production, and its use as a curing agent for epoxy resins.
  • Epoxy resin systems containing such an etheramine mixture may be suitable for preparing, for example, self-leveling (and self-curing) floor coatings, high-build table tops, and other decorative coating applications.
  • Polyetheramines are widely used as curing agents for epoxy resins or as reactants in the synthesis of polyamides or polyureas.
  • Such polyetheramines are generally produced by the reaction of an alkylene oxide with an alcohol to form a polyoxyalkylene polyol and then subsequent conversion of the hydroxyl groups to amine groups by reductive amination.
  • EP 0572176 A1 and EP 2515643 A1 are dealing with etheramine mixtures which are used as curing agents for curable epoxy resins.
  • etheramine mixtures which are used as curing agents for curable epoxy resins.
  • the term "about” is used to indicate that a value includes the inherent variation of error for the quantifying device, mechanism, or method, or the inherent variation that exists among the subject(s) to be measured.
  • the designated value to which it refers may vary by plus or minus ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent, or one or more fractions therebetween.
  • At least one will be understood to include one as well as any quantity more than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc.
  • the term “at least one” may extend up to 100 or 1000 or more depending on the term to which it refers.
  • the quantities of 100/1000 are not to be considered as limiting since lower or higher limits may also produce satisfactory results.
  • the phrase "at least one of X, Y, and Z" will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y, and Z.
  • the phrase “at least one of X and Y” will be understood to include X alone, Y alone, as well as any combination of X and Y.
  • the phrase “at least one of” can be used with any number of components and have the similar meanings as set forth above.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), "including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • phrases "or combinations thereof” and “and combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term.
  • “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC and, if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • expressly included are combinations that contain repeats of one or more items or terms such as BB, AAA, CC, AABB, AACC, ABCCCC, CBBAAA, CABBB, and so forth.
  • % by weight As used herein, the terms “% by weight”, “wt. %”, “weight percent”, or “percentage by weight” are used interchangeably.
  • room temperature refers to the ambient temperature of the surrounding work environment (e.g., the temperature of the area, building or room where the curable composition is used), exclusive of any temperature changes that occur as a result of the direct application of heat to the curable composition to facilitate curing.
  • Room temperature is typically between about 5 °C to about 30 °C, or between about 10 °C and about 30 °C, or more specifically about 15 °C and about 25 °C, and or even more specifically about 20 °C to about 25 °C.
  • the present disclosure is directed to an etheramine mixture comprising one or more polyether diamines of formula (I): wherein: R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; wherein the hydrophobic diol has 6 to 15 carbon atoms; n is in a range of from 1 to 3; x and y are each in a range of from 1 to 9; and the sum of x and y is in a range of from 2 to 10.
  • R is a radical of a hydrophobic diol after removal of the two hydroxyl groups from the hydrophobic diol; wherein the hydrophobic diol has 6 to 15 carbon atoms; n is in a range of from 1 to 3; x and y are each in a range of from 1 to 9; and the sum of x and y is in a range of from 2 to 10.
  • the hydrophobic diol can be selected from a cycloaliphatic diol, a hydrogenated aromatic diol, a linear alkyl diol, and combinations thereof.
  • the hydrophobic diol comprises 6 to 15 carbon atoms. In another embodiment, the hydrophobic diol comprises 6 to 12 carbon atoms. In yet another embodiment, the hydrophobic diol comprises 6 to 10 carbon atoms.
  • Non-limiting examples of the cycloaliphatic diol include cyclohexane diols, such as, for example but without limitation, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,5-cyclooctanediol, hydrogenated derivatives of: bisphenol F, bisphenol A, hydroquinone, catechol, and resorcinol, and combinations thereof.
  • One particularly preferred cyclohexane diol is 1,4-cyclohexanedimethanol (CHDM).
  • linear alkyl diol examples include 1,6-hexanediol, 1,7-heptane diol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.
  • One particularly preferred linear alkyl diol is 1,8-octanediol.
  • the hydrophobic diol can be neopentyl glycol.
  • x and y can be in a range of from 2 to 8, or from 2 to 7, or from 3 to 7, or from 3 to 6, or from 4 to 5, or about 4.5.
  • n is in a range of from 1 to 2.
  • R in formula (I) is a radical of the hydrophobic diol 1,4-cyclohexanedimethanol after removal of the two hydroxyl groups, as represented by formula (II): wherein x, y, and n are the same as those previously defined for formula (I).
  • the amine groups of the one or more polyether diamines of formula (I) are at least 60%, or at least 65%, or at least 70%, or at least 75% primary amines. In one particular embodiment, about 75 to 80% of the amine groups of the one or more polyether diamines of formula (I) are primary amines.
  • the present disclosure is also directed to a method for producing an etheramine mixture comprising: (i) charging a hydrophobic diol (as described above) to an alkoxylation reaction zone; (ii) contacting the hydrophobic diol with an ethylene oxide in the alkoxylation reaction zone to provide a precursor diol, wherein the molar ratio of ethylene oxide to the hydrophobic diol is in a range of from greater than 1:1 to 10:1, or from greater than 2:1 to 10:1, or from 2:1 to 9:1, or from 2:1 to 8:1, or from 2:1 to 7:1, or from 2:1 to 6:1, or from 3:1 to 6:1, or from 3:1 to 5:1, or from 4:1 to 5-1, or 4.5:1; and (iii) charging the precursor diol to a reductive amination zone and reductively aminating the precursor diol to form the etheramine mixture containing one or more polyether diamines of formula (I).
  • the amount of time the hydrophobic diol is contacted with the alkylene oxide is such that it is sufficient to form the precursor diol and in some embodiments may range from about 0.5 hours to about 24 hours.
  • the alkoxylation reaction zone can be a closed reaction vessel, wherein alkoxylation is carried out under elevated temperature and pressure and in the presence of a base catalyst.
  • alkoxylation may be conducted at a temperature ranging from about 50°C to about 150°C and a pressure ranging from 275.8 KPa (40 psi) to 689.5 KPa (100 psi)
  • the base catalyst may be any alkaline compound customarily used for base-catalyzed reactions, for example, an alkali metal hydroxide such as sodium hydroxide, lithium hydroxide, potassium hydroxide, or cesium hydroxide, or a tertiary amine, such as dimethyl cyclohexylamine or 1,1,3,3-tetramethylguanidine.
  • the resulting mixture may be vacuum stripped to remove any unnecessary components, such as excess unreacted alkylene oxide, water and/or base catalyst, while leaving the resulting precursor diol.
  • the precursor diol may be neutralized with any suitable acid or chemical adsorbent, such as for example, oxalic acid or magnesium silicate, and filtered for the removal of insoluble materials.
  • any suitable acid or chemical adsorbent such as for example, oxalic acid or magnesium silicate
  • the step of reductively aminating the precursor diol is carried out in the presence of a reductive amination catalyst, hydrogen, and ammonia. More particularly, the step of reductively aminating the precursor diol includes charging the precursor diol to a reductive amination zone where it is brought into contact with a reductive amination catalyst, sometimes referred to as a hydrogenation-dehydrogenation catalyst, and reductively aminated in the presence of ammonia and hydrogen under reductive amination conditions.
  • a reductive amination catalyst sometimes referred to as a hydrogenation-dehydrogenation catalyst
  • Such reductive amination conditions may include, for example, a temperature within the range of 150°C to 275°C and a pressure within the range of 3447.4 KPa (500 psi) to 34474 KPa (5000 psi) with temperatures within the range of 180°C to 220°C and pressures within the range of 10.34 MPa (1500 psi) to 17.23 MPa (2500 psi) being preferred.
  • any suitable hydrogenation catalyst may be used for the reductive amination step, such as those described in U.S. Pat. No. 3,654,370 .
  • the hydrogenation catalyst may comprise one or more of the metals of group VIIIB of the Periodic Table, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, mixed with one or more metals of group VIB of the Periodic Table such as chromium, molybdenum or tungsten.
  • a promoter from group IB of the Periodic Table, such as copper, may also be included.
  • a catalyst may be used comprising from about 60 mole percent to about 85 mole percent of nickel, about 14 mole percent to about 37 mole percent of copper and about 1 mole percent to about 5 mole percent of chromium (as chromia), such as a catalyst of the type disclosed in U.S. Pat. No. 3,152,998 .
  • a catalyst of the type disclosed in U.S. Pat. No. 4,014,933 may be used containing from about 70% by weight to about 95% by weight of a mixture of cobalt and nickel and from about 5% by weight to about 30% by weight of iron.
  • 4,152,353 may be used, comprising nickel, copper and a third component which may be iron, zinc, zirconium or a mixture thereof, for example, a catalyst containing from about 20% by weight to about 49% by weight of nickel, about 36% by weight to about 79% by weight of copper and about 1% by weight to about 15% by weight of iron, zinc, zirconium or a mixture thereof.
  • a catalyst of the type described in U.S. Pat. No. 4,766,245 may be used comprising about 60% by weight to about 75% by weight of nickel and about 25% by weight to about 40% by weight of aluminum.
  • the reductive amination is preferably conducted on a continuous basis with the precursor diol, ammonia and hydrogen being continuously charged to a reactor containing a fixed bed of reductive amination catalyst and with the reaction product being continually withdrawn.
  • the reaction product is suitably depressured so as to recover excess hydrogen and ammonia for recycle and is then fractionated to remove byproduct water of reaction and to provide the desired etheramine mixture.
  • the reductive amination conditions to be utilized may suitably include the use of from 4 moles to 150 moles of ammonia per hydroxyl equivalent of precursor diol feedstock.
  • Hydrogen is preferably used in an amount ranging from 0.5 mole equivalents to 10 mole equivalents of hydrogen per hydroxyl equivalent of precursor diol feedstock.
  • the contact times within the reaction zone, when the reaction is conducted on a batch basis, may suitably be within the range of from 0.1 hours to 6 hours and more preferably from 0.15 hours to 2 hours.
  • reaction rates may suitably be from 0.1 grams to 2 grams of feedstock per hour per cubic centimeter of catalyst and, more preferably, from 0.3 grams to 1.6 grams of feedstock per hour per cubic centimeter of catalyst.
  • the reductive amination may be conducted in the presence of 1 mole to 200 moles of ammonia per mole of precursor diol and more preferably, from 4 moles to 130 moles of ammonia per mole of precursor diol. From 0.1 moles to 50 moles of hydrogen per mole of precursor diol may be employed and, more preferably, from 1 mole to 25 moles of hydrogen per mole of precursor diol.
  • the present disclosure is directed to the etheramine mixture produced according to the method as presently disclosed.
  • the etheramine mixture according to the present disclosure may be used as a curing agent for epoxy resins which can be utilized in a variety of industrial applications, including the preparation of, for example, self-leveling (and self-curing) floor coatings, high-build table tops, and other decorative coating applications.
  • the present disclosure is directed to an epoxy resin system comprising an epoxy resin and the etheramine mixture as disclosed herein.
  • the present disclosure is also directed to a method of forming an epoxy resin system comprising contacting an epoxy resin with the presently disclosed etheramine mixture.
  • the epoxy resin may be any one or mixture of reactive epoxy resin(s) having a 1,2-epoxy equivalency (functionality), on the average, of at least 1 epoxide groups per molecule, preferably at least 1.3 epoxide groups per molecule, and more preferably at least 1.6 epoxide groups per molecule, and even more preferably with epoxy resins having a functionality of at least 2 epoxy groups per molecule such that the mixture will polymerize to form a useful material with the polyether diamines of the presently disclosed etheramine mixture or its blend with other amine hardeners.
  • reactive epoxy resin(s) having a 1,2-epoxy equivalency (functionality), on the average of at least 1 epoxide groups per molecule, preferably at least 1.3 epoxide groups per molecule, and more preferably at least 1.6 epoxide groups per molecule, and even more preferably with epoxy resins having a functionality of at least 2 epoxy groups per molecule such that the mixture will polymerize
  • the epoxy resin has a functionality on the average ranging from at least 1.3 epoxide groups per molecule to about 8 epoxide groups per molecule, preferably from at least about 1.6 epoxide groups per molecule to about 5 epoxide groups per molecule.
  • the epoxy resin can be saturated or unsaturated, linear or branched, aliphatic, cycloaliphatic, aromatic or heterocyclic, and may bear substituents such as bromine or fluorine. It may be monomeric or polymeric, liquid or solid, but is preferably liquid or a low melting solid at room temperature.
  • the epoxy resin is a polyglycidyl epoxy compound, such as a polyglycidyl ether, poly( ⁇ -methylglycidyl) ether, polyglycidyl ester or poly( ⁇ -methylglycidyl) ester.
  • a polyglycidyl epoxy compound such as a polyglycidyl ether, poly( ⁇ -methylglycidyl) ether, polyglycidyl ester or poly( ⁇ -methylglycidyl) ester.
  • ethers may be obtained by reacting a compound having at least one free alcoholic hydroxyl group and/or phenolic hydroxyl group with a suitably substituted epichlorohydrin under alkaline conditions or in the presence of an acidic catalyst followed by alkali treatment.
  • the alcohols may be, for example, acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1,2-diol, or poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bistrimethylolpropane, pentaerythritol and sorbitol.
  • acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly(oxyethylene) glycols, propane-1,2-diol, or poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly(oxyt
  • Suitable glycidyl ethers may also be obtained, however, from cycloaliphatic alcohols, such as 1,3- or 1,4-dihydroxycyclohexane, bis(4-hydroxycyclo-hexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1,1-bis(hydroxymethyl)cyclohex-3-ene, or they may possess aromatic rings, such as N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)diphenylmethane.
  • cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis(4-hydroxycyclo-hexyl)methane, 2,2-bis(4-hydroxycyclohexyl)propane or 1,1-bis(hydroxymethyl)cyclohex-3-ene, or they may possess aromatic rings, such as N,N-bis(2-hydroxyethyl)aniline
  • polyglycidyl ethers or poly( ⁇ -methylglycidyl) ethers include those based on monocyclic phenols, for example, on resorcinol or hydroquinone, on polycyclic phenols, for example, on bis(4-hydroxyphenyl)methane (Bisphenol F), 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A), bis(4-hydroxyphenyl)S (Bisphenol S), alkoxylated Bisphenol A, F or S, triol extended Bisphenol A, F or S and brominated Bisphenols A, F or S, hydrogenated Bisphenol A, F or S, glycidyl ethers of phenols and phenols with pendant groups or chains, on condensation products, obtained under acidic conditions, of phenols or cresols with formaldehyde, such as phenol novolaks and cresol novolaks, or on siloxane diglycidyls.
  • Polyglycidyl esters and poly( ⁇ -methylglycidyl) esters may be produced by reacting epichlorohydrin or glycerol dichlorohydrin or ⁇ -methylepichlorohydrin with a polycarboxylic acid compound. The reaction is expediently carried out in the presence of bases.
  • the polycarboxylic acid compounds may be, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid.
  • cycloaliphatic polycarboxylic acids for example tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • aromatic polycarboxylic acids such as, for example, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid, or else carboxyl-terminated adducts, for example of trimellitic acid and polyols, for example glycerol or 2,2-bis(4-hydroxycyclohexyl)propane, can be used.
  • the epoxy resin is a non-glycidyl epoxy compound.
  • Non-glycidyl epoxy compounds may be linear, branched, or cyclic in structure.
  • Others include an epoxy-containing compound with at least one epoxycyclohexyl group that is bonded directly or indirectly to a group containing at least one silicon atom. Examples are disclosed in U.S. Pat. No. 5,639,413 .
  • Still others include epoxides which contain one or more cyclohexene oxide groups and epoxides which contain one or more cyclopentene oxide groups.
  • non-glycidyl epoxy compound's include the following difunctional non-glycidyl epoxide compounds in which the epoxide groups form part of an alicyclic or heterocyclic ring system: bis(2,3-epoxycyclopentyl) ether, 1,2-bis(2,3-epoxycyclopentyloxy)ethane, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, di(3,4-epoxycyclohexylmethyl)hexanedioate, di(3,4-epoxy-6-methylcyclohexylmethyl) hexanedioate, ethylenebis(3,4-epoxycyclohexanecarboxylate), ethanediol di(3,4-epoxycyclol di
  • the epoxy resin is an epoxy novolac compound obtained by the reaction of, preferably in the presence of a basic catalyst such as sodium or potassium hydroxide, an epihalohydrin, such as epichlorohydrin, with a resinous condensate of an aldehyde, such as formaldehyde and either a monohydric phenol or polyhydric phenol.
  • a basic catalyst such as sodium or potassium hydroxide
  • an epihalohydrin such as epichlorohydrin
  • an aldehyde such as formaldehyde and either a monohydric phenol or polyhydric phenol.
  • the epoxy resin is a poly(N-glycidyl) compound or poly(S-glycidyl) compound.
  • Poly(N-glycidyl) compounds are obtainable, for example, by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two amine hydrogen atoms. These amines may be, for example, n-butylamine, aniline, toluidine, m-xylylenediamine, bis(4-aminophenyl)methane or bis(4-methylaminophenyl)methane.
  • poly(N-glycidyl) compounds include N,N'-diglycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or 1,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins, such as of 5,5-dimethylhydantoin.
  • poly(S-glycidyl) compounds are di-S-glycidyl derivatives derived from dithiols, for example ethane-1,2-dithiol or bis(4-mercaptomethylphenyl) ether.
  • epoxy-containing compounds in which the 1,2-epoxide groups are attached to different heteroatoms or functional groups.
  • these compounds include the N,N,O-triglycidyl derivative of 4-aminophenol, the glycidyl ether/glycidyl ester of salicylic acid, N-glycidyl-N'-(2-glycidyloxypropyl)-5,5-dimethylhydantoin or2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylhydantoin-3-yl)propane.
  • epoxide derivatives may be employed, such as vinyl cyclohexene dioxide, limonene dioxide, limonene monoxide, vinyl cyclohexene monoxide, 3,4-epoxycyclohexlmethyl acrylate, 3,4-epoxy-6-methyl cyclohexylmethyl 9,10-epoxystearate, and 1,2-bis(2,3-epoxy-2-methylpropoxy)ethane.
  • oxetanes or liquid pre-reacted adducts of epoxy-containing compounds such as those mentioned above, with hardeners for the epoxy resins.
  • the epoxy resin system may further contain customary additives and auxiliaries such as stabilizers, modifiers, antifoaming agents, toughening agents, accelerators, co-curing agents, leveling agents, thickening agents, flame retardants, antioxidants, pigments, dyes, fillers, and combinations thereof.
  • an accelerator such as guanidine or a derivative thereof may be used in the epoxy resin system.
  • guanidine derivatives include without limitation, an alkylguanidine such as dimethylguanidine or tetramethyl guanidine, or a guanidinium salt derived from any of these.
  • guanidinium salts include without limitation, guanidine carbonates, guanidine acetates, and guanidine nitrates.
  • the etheramine mixtures may not require the use of co-curing agent, such as cycloaliphatic diamines such as isophorone diamine. In these embodiments, fewer materials would be needed to manufacture the epoxy resin as well as less energy needed to reach the lower cure temperature.
  • co-curing agent such as cycloaliphatic diamines such as isophorone diamine.
  • the epoxy resin system may be applied to one or more surfaces of an article, for example, brushing, spraying, dipping, electrostatic spraying, etc., the epoxy resin system thereto, and then subjecting the coated article to conditions suitable to cause the epoxy resin system to cure.
  • the above-described epoxy resin system once prepared and/or applied to one or more surfaces, may then be subjected to conditions sufficient to cause the epoxy resin system to cure.
  • the epoxy resin system is substantially cured at room temperature. It was surprisingly found that the presently disclosed etheramine mixture has low viscosity and epoxy resin systems containing such are capable of being substantially cured at room temperature within about 12 hours without additional heating. In one particular embodiment, the epoxy resin system is substantially cured at a temperature ranging from about 20 °C to about 30 °C for a time ranging from about 6 to about 24 hours, or from about 6 to about 22 hours, or from about 6 to about 20 hours, or from about 12 to about 24 hours, or from about 16 to about 22 hours, or from about 6 to 12 hours, or any span of time between the ranges set forth herein.
  • the present disclosure in one aspect, is directed to a composite formed by curing the epoxy resin system as disclosed herein.
  • the epoxy resin system is substantially free of methyl 3-methoxypropionate ("MMP") and/or benzyl alcohol.
  • An exemplary etheramine mixture was prepared by adding about 3.27 kg (7.2 lbs.) of 1,4-cyclohexanedimethanol (CHDM) and 100 g of dimethyl cyclohexylamine (DMCHA) to a four-gallon reactor kettle.
  • CHDM 1,4-cyclohexanedimethanol
  • DMCHA dimethyl cyclohexylamine
  • EO ethylene oxide
  • the mixture of CHDM, DMCHA, and EO was then digested at 100 °C for 2 to 3 hours to form a digested mixture containing a polyetherdiol from the reaction of CHDM and EO.
  • the digested mixture was stripped with nitrogen and then subjected to a vacuum at 100 °C to remove excess EO and DMCHA.
  • the remaining polyetherdiol was packaged in a one-gallon jug.
  • the polyetherdiol was a clear, mobile liquid with a hydroxyl number of 363, water content of 0.07 wt.%, and a weight average molecular weight of 309 Daltons.
  • the polyetherdiol from the reaction of CHDM and EO was then subjected to continuous, reductive amination over a nickel/copper/zirconia catalyst in an up-flow reactor, with hydrogen and ammonia, at a temperature of about 200 °C and pressure of about 2000 psi for about 24 to 36 hours to form the etheramine mixture comprising one or more polyether diamines.
  • the ethylene mixture was collected in gallon containers, which were vented of excess ammonia and vacuum stripped down to about 1-2 mmHg to remove water and residual ammonia.
  • the final ethylene mixture was a very low-colored liquid with low viscosity and showed complete solubility in water.
  • the etheramine mixture had a total amine value of 5.17 meq./g. and an amine conversion of 96.4%, 78.5% of which was primary amines and 21.5% of mostly secondary amines.
  • the weight average molecular weight of the etheramine mixture was about 650 Daltons and the calculated amine hydrogen equivalent weight (AHEW) was 109.
  • Table 1 Various properties of the three examples are set forth in Table 1 below. The three examples are differentiated by the molar ratios of EO to CHDM. Table 1 Molar Ratio of EO:CHDM 2:1 3.33:1 4:1 AHEW 80 101 109 Primary Amine, % 76 75 77 Secondary Amine, % 23 25 22 Viscosity, cps @ 25°C 150 195 162
  • a curable epoxy resin system was prepared by adding (i) 59 g of the above-described etheramine mixture prepared using a 4:1 molar ratio of EO to CHDM, and (ii) 100 g of ARALDITE ® 6010 epoxy resin available from Huntsman Corporation or one of its affiliates (The Woodlands, TX). The resulting mixture was stirred well with a spatula until a clear, homogeneous solution was formed. The homogeneous solution was then poured into molds as well as over a wooden surface with an attached picture. After curing overnight at room temperature, both the castings and wood coating were clear, hard materials, which were glossy on the surface without any apparent defects such as amine-blush or water-spotting.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)

Claims (9)

  1. Etheraminmischung, bestehend aus einem oder mehreren Polyetherdiaminen der Formel (I): wobei:
    R ein Radikal eines hydrophoben Diols nach Entfernung der beiden Hydroxylgruppen aus dem hydrophoben Diol ist, wobei das hydrophobe Diol 6 bis 15 Kohlenstoffatome aufweist;
    n im Bereich von 1 bis 3 liegt;
    x und y jeweils in einem Bereich von 1 bis 9 liegen; und
    die Summe von x und y in einem Bereich von 2 bis 10 liegt.
  2. Etheraminmischung nach Anspruch 1, wobei das hydrophobe Diol aus einem cycloaliphatischen Diol, einem hydrierten aromatischen Diol, einem linearen Alkyldiol oder einer Kombination davon ausgewählt ist und wobei das hydrophobe Diol mehr bevorzugt ein Cyclohexandiol ist.
  3. Etheraminmischung nach einem der vorstehenden Ansprüche, wobei die Summe von x und y in einem Bereich von 3 bis 6 liegt.
  4. Verfahren zum Herstellen einer Etheraminmischung, umfassend:
    - Einbringen eines hydrophoben Diols in eine Alkoxylierungsreaktionszone;
    - Inkontaktbringen des hydrophoben Diols mit einem Ethylenoxid in der Alkoxylierungsreaktionszone, um ein Vorläuferdiol bereitzustellen, wobei das Molverhältnis von Ethylenoxid zu hydrophobem Diol in einem Bereich von größer als 1:1 bis 10:1 liegt; und
    - Einbringen des Vorläuferdiols in eine reduktive Aminierungszone und reduktives Aminieren des Vorläuferdiols, um eine Etheraminmischung nach einem der vorstehenden Ansprüche 1 bis 3 zu bilden.
  5. Verfahren nach Anspruch 4, wobei das Molverhältnis von Ethylenoxid zu hydrophobem Diol in einem Bereich von größer als 2:1 bis 10:1 liegt.
  6. Verfahren zum Herstellen eines Epoxidharzsystems, umfassend:
    - Bereitstellen der Etheraminmischung nach einem der vorstehenden Ansprüche 1-3;
    - Bereitstellen eines Epoxidharzes;
    - Inkontaktbringen der Etheraminmischung und des Epoxidharzes, um ein Epoxidharzsystem zu bilden.
  7. Verfahren zum Herstellen eines gehärteten Epoxidharzsystems, umfassend:
    - Bereitstellen einer Etheraminmischung nach einem der vorstehenden Ansprüche 1-3;
    - Bereitstellen eines Epoxidharzes;
    - Inkontaktbringen der Etheraminmischung und des Epoxidharzes, um ein Epoxidharzsystem zu bilden; und
    - Härten des Epoxidharzsystems, wobei der Schritt des Härtens des Epoxidharzsystems das Aussetzen des Epoxidharzsystems einer Temperatur im Bereich von etwa 5 °C bis 30 °C für eine Zeit im Bereich von 6 bis 24 Stunden umfasst.
  8. Etheraminmischung, hergestellt durch ein Verfahren nach Anspruch 4 oder 5.
  9. Verbundwerkstoff, gebildet durch das Verfahren nach Anspruch 7.
EP19772328.1A 2018-03-19 2019-03-18 Etheraminmischung bestehend aus polyetherdiaminen und verfahren zu ihrer herstellung und verwendung Active EP3768743B1 (de)

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US5241016A (en) * 1992-05-29 1993-08-31 Texaco Chemical Company Epoxy adhesives containing aminated, long chain monoepoxide capped polyols
JPH08311194A (ja) * 1995-05-22 1996-11-26 Huntsman Corp ポリエーテルアミドの界面活性剤
JP2001181384A (ja) 1999-12-27 2001-07-03 Tosoh Corp ポリオキシアルキレンアミン製造触媒の再賦活化方法
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EP2842936A1 (de) * 2013-08-26 2015-03-04 Basf Se Etheramine auf Basis von alkoxyliertem Glycerin oder Trimethylolpropan
AR098050A1 (es) * 2013-10-18 2016-04-27 Huntsman Petrochemical Llc Eteraminas con mayor estabilidad térmica y su uso como curativos o intermediarios para la síntesis de polímeros
CN105705015A (zh) * 2013-11-05 2016-06-22 亨斯迈石油化学有限责任公司 醚胺和它们作为固化剂或聚合物合成的中间体的用途
BR112017005841A2 (pt) 2014-09-25 2018-01-30 Basf Se mistura de eteramina, processo para a produção de uma mistura de eteramina, e, uso de uma mistura de eteramina.

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